JP2013163747A - Liquid resin composition for sealing semiconductor, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid resin composition for sealing a semiconductor, which is excellent in balance among flowability, fracture toughness value and elastic modulus, and to provide a semiconductor device using the same, which is excellent in reflow resistance and thereby high in connection reliability during a heat cycle test.SOLUTION: A liquid resin composition for sealing a semiconductor includes an epoxy resin (A), an amine-based curing agent (B), and an inorganic filler (C). The epoxy resin (A) contains an epoxy resin (A1) which is liquid at 25°C and an aromatic glycidylamine-type epoxy resin (A2), the content of the inorganic filler (C) is 30 to 75 wt.%, and the fracture toughness value of a cured material of the liquid resin composition is 2.0 to 3.5 MPa-m0.5.

Description

  The present invention relates to a liquid resin composition for semiconductor encapsulation and a semiconductor device using the same.

Reflecting the recent trend of miniaturization, weight reduction, and high integration of electronic devices, the size of semiconductor elements or other electronic components has become smaller and the wiring has become finer. In order to electrically connect such a semiconductor element or other electronic component to the mounting substrate and operate at high speed, a bump electrode is formed on the semiconductor element or other electronic component and mounted by this bump. A mounting method called flip-chip connection, in which the substrates are joined together, is adopted.
However, the bump which is a fine connection part of the flip chip connection is weak in external strength, and in order to protect this, the semiconductor element is utilized by utilizing capillary action in the gap between the semiconductor element or other electronic components and the mounting substrate. Alternatively, a liquid resin composition called an underfill material is filled from the side part of another electronic component and sealed by curing.
Similarly, in the mounting of BGA (Ball Grid Array) and CSP (Chip size Package), an underfill material is used to reinforce the connection portion in order to improve the connection strength of the solder ball.
In this flip chip connection or BGA or CSP mounting, stress or strain due to hardening accumulates in a portion (hereinafter referred to as a fillet) where an underfill material protrudes around a semiconductor element or other electronic component, and a bump joint. In addition, peeling or cracking may occur due to thermal shock, thermal expansion / contraction, deformation due to moisture absorption, heat treatment, or the like. Separation and cracks generated in the fillet portion and the bump bonding portion are seriously related to the connection reliability between the bump bonding portions and have become serious problems. In addition, the solder forming the bump electrode is changed from eutectic solder to lead-free solder, the reflow temperature during mounting becomes higher, the thermal stress applied to the semiconductor device of the semiconductor element or other electronic component increases, Since lead-free solder is inferior in mechanical strength to crystal solder, the conventional underfill material has a problem that peeling and cracking of the fillet part, peeling and cracking of the bump joint part, etc. are likely to occur.
Further, as the number of bumps increases, the bump pitch and bump height are reduced, and as a result, the gap is being narrowed. With higher integration, the chip size increases, and the underfill material is also required to have a characteristic of flowing over a large area with a narrow gap.

  For such problems, attempts have been made to reduce the stress and toughness of the underfill material. Examples of such techniques include a composition in which an inorganic filler and rubber particles are added to a liquid epoxy resin (see, for example, Patent Documents 1 and 2), an inorganic filler, an elastomer, and an aromatic amine curing agent in a liquid epoxy resin. (For example, refer patent document 3) using this. However, the conventional method has poor pouring properties into the gap, and the effect of reducing stress and improving toughness is not sufficient.

JP 2006-169395 A JP 2007-182560 A JP 2006-233127 A

The present invention provides a liquid resin composition for encapsulating a semiconductor that has an excellent balance of fluidity, fracture toughness, and elastic modulus, and a semiconductor device having high connection reliability during a temperature cycle test using the same.

The present invention
[1] A liquid resin composition for semiconductor encapsulation containing an epoxy resin (A), an amine curing agent (B), and an inorganic filler (C), wherein the epoxy resin (A) is at 25 ° C. Including a liquid epoxy resin (A1) and an aromatic glycidylamine type epoxy resin (A2), wherein the content of the inorganic filler (C) is 30 wt% or more and 75 wt% or less, and the liquid for semiconductor encapsulation A liquid resin composition for encapsulating a semiconductor, wherein the fracture toughness value of the cured product of the resin composition is 2.0 MPa · m ^ 0.5 or more and 3.5 MPa · m ^ 0.5 or less,
[2] The liquid resin composition for semiconductor encapsulation according to [1], wherein an elastic modulus at 240 ° C. measured by a dynamic viscoelasticity measuring apparatus of a cured product of the liquid resin composition for semiconductor encapsulation is 120 MPa or more, [3] For semiconductor encapsulation according to [1] or [2], wherein the glass transition temperature measured in a dynamic viscoelasticity measuring apparatus for a cured product of the liquid resin composition for semiconductor encapsulation is 120 ° C. or higher and 150 ° C. or lower. Liquid resin composition,
[4] The liquid resin composition for semiconductor encapsulation according to any one of [1] to [3], which contains a compound represented by the following general formula (1) as the aromatic glycidylamine type epoxy resin (A2). ,

（一般式（１）において、Ｒ１、Ｒ２、Ｒ３は、互いに独立して、水素原子、又は炭素数１〜６の炭化水素基であり、ｍ１は０〜４の整数であり、ｎ１は０〜５の整数である。）［５］芳香族グリシジルアミン型エポキシ樹脂（Ａ２）として、上記一般式（１）で表わされる化合物及び下記一般式（２）で表わされる化合物を含む［１］ないし［４］のいずれか１項に記載の半導体封止用液状樹脂組成物、

(In General Formula (1), R1, R2, and R3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m1 is an integer of 0 to 4, and n1 is 0 to 0. [5] The aromatic glycidylamine type epoxy resin (A2) includes a compound represented by the above general formula (1) and a compound represented by the following general formula (2) [1] to [ 4] The liquid resin composition for semiconductor encapsulation according to any one of

（一般式（２）において、Ｒ４は、互いに独立して、水素原子、又は炭素数１〜６の炭化水素基であり、ｍ４は０〜４の整数である。）
［６］アミン系硬化剤（Ｂ）として、下記一般式（３）で表わされる化合物及び／又はジエチルトルエンジアミンを含む［１］ないし［５］のいずれか１項に記載の半導体封止用
液状樹脂組成物、

(In General formula (2), R4 is a hydrogen atom or a C1-C6 hydrocarbon group mutually independently, and m4 is an integer of 0-4.)
[6] The liquid for semiconductor encapsulation according to any one of [1] to [5], which contains a compound represented by the following general formula (3) and / or diethyltoluenediamine as the amine-based curing agent (B). Resin composition,

（一般式（３）において、Ｒ５、Ｒ６は、互いに独立して、水素原子、又は炭素数１〜６の炭化水素基であり、ｍ５は０〜３の整数であり、ｎ３は０〜１０の整数である。）
［７］さらに、低応力剤（Ｄ）を含む［１］ないし［６］のいずれか１項に記載の半導体封止用液状樹脂組成物、
［８］低応力剤（Ｄ）として、エポキシ化ポリブタジエンを含む［１］ないし［７］のいずれか１項に記載の半導体封止用液状樹脂組成物、
［９］電子部品と電子部品搭載用基板とを含み、電子部品と電子部品搭載用基板との間に間隙を有する半導体装置であって、電子部品と電子部品搭載用基板との間隙が、［１］ないし［８］のいずれか１項に記載の半導体封止用液状樹脂組成物の硬化物によって、充填接合させてなることを特徴とする半導体装置、
である。

(In General Formula (3), R5 and R6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m5 is an integer of 0 to 3, and n3 is an integer of 0 to 10. (It is an integer.)
[7] The liquid resin composition for semiconductor encapsulation according to any one of [1] to [6], further comprising a low stress agent (D),
[8] The liquid resin composition for semiconductor encapsulation according to any one of [1] to [7], comprising epoxidized polybutadiene as the low stress agent (D),
[9] A semiconductor device including an electronic component and an electronic component mounting substrate, and having a gap between the electronic component and the electronic component mounting substrate, wherein the gap between the electronic component and the electronic component mounting substrate is [ 1] to [8], a semiconductor device characterized by being filled and bonded with a cured product of the liquid resin composition for sealing a semiconductor according to any one of
It is.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid resin composition for semiconductor sealing which is excellent in balance of fluidity | liquidity, fracture toughness value, and elastic modulus, and the semiconductor device excellent in reflow resistance with high connection reliability at the time of a temperature cycle test using the same Can be obtained.

  This invention is the liquid resin composition for semiconductor sealing containing an epoxy resin (A), an amine type hardening | curing agent (B), and an inorganic filler (C), Comprising: An epoxy resin (A) is 25 degreeC. A liquid resin composition for encapsulating a semiconductor, comprising a liquid epoxy resin (A1) and an aromatic glycidylamine type epoxy resin (A2), wherein the content of the inorganic filler (C) is 30 wt% to 75 wt% The fracture toughness value of the cured product is 2.0 MPa · m ^ 0.5 or more and 3.5 MPa · m ^ 0.5 or less. According to another aspect of the present invention, there is provided a semiconductor device including an electronic component and an electronic component mounting substrate, wherein the electronic component and the electronic component mounting substrate have a gap between the electronic component and the electronic component mounting substrate. The gap is filled and bonded with a cured product of the liquid resin composition for semiconductor encapsulation. Hereinafter, the present invention will be described in detail.

  In the liquid resin composition for semiconductor encapsulation of the present invention, an epoxy resin (A1) and an aromatic glycidylamine type epoxy resin (A2) that are liquid at 25 ° C. are used as the epoxy resin (A).

Examples of the epoxy resin (A1) that is liquid at 25 ° C. used in the present invention include bisphenol A type epoxy resins and hydrogenated products thereof, bisphenol F type epoxy resins and hydrogenated products thereof, and bisphenol S type epoxy resins. Bisphenol AD epoxy resin, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, trimethylolpropane diglycidyl ether , Polypropylene glycol diglycidyl ether, hydroquinone diglycidyl ether, ter-butyl-hydroquinone diglycidyl ether, ter-butyl-phenyl diglycidyl ether, resorcinol diglycol Diethers such as dil ether, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl diglycidyl ether, 4,4′-dihydroxybiphenyl diglycidyl ether, 1,6-dihydroxybiphenyl diglycidyl ether, etc. Examples thereof include glycidyl ether type epoxy resins, triglycidyl ether type epoxy resins such as phloroglicidyl triglycidyl ether, phenol novolac type epoxy resins, bromine-based phenol novolac type epoxy resins, diallyl bisphenol A diglycidyl type epoxy resins and the like.

  In the present invention, bisphenol A type epoxy resin and bisphenol F type epoxy resin are preferable from the viewpoint of reactivity and heat resistance, and bisphenol F type epoxy resin is more preferable from the viewpoint of fluidity. These may be used alone or in combination of two or more. Furthermore, since the aspect of the present invention is a liquid resin composition for semiconductor encapsulation used as an underfill material, it may be finally liquid at 25 ° C. as an epoxy resin, and even if it is a solid epoxy resin at 25 ° C. What is necessary is just to make it melt | dissolve in a liquid epoxy resin at 0 degreeC and, as a result, a liquid state.

  The resin viscosity of the epoxy resin (A1) that is liquid at 25 ° C. is preferably from 50 mPa · s to 15,000 mPa · s, and preferably from 1000 mPa · s to 3000 mPa · s at 25 ° C. Is more preferable. When the lower limit of the viscosity is within the above range, the resulting resin-sealing liquid resin composition has good curability. On the other hand, when the upper limit is in the above range, the fluidity of the obtained liquid resin composition for semiconductor encapsulation becomes good.

  The epoxy group equivalent of the epoxy resin (A1) which is liquid at 25 ° C. is preferably 140 g / eq or more and 190 g / eq or less, and more preferably 150 g / eq or more and 170 g / eq or less. When the epoxy group equivalent is within the above range, the obtained liquid resin composition for encapsulating a semiconductor has good reactivity.

  The aromatic glycidylamine type epoxy resin (A2) used in the present invention is an epoxy resin having a glycidyl group bonded to a nitrogen atom, and further has at least one aromatic ring in the molecule. Examples of the aromatic glycidylamine type epoxy resin (A2) include N, N-diglycidylaniline, N, N-diglycidyl-2-methylbenzenamine, N, N-diglycidyl-4- (glycidyloxy) aniline, N , N-diglycidyl-3- (glycidyloxy) aniline, N, N-diglycidyl-3- (glycidyloxy) -5-methylaniline, N, N-diglycidyl-4- (glycidyloxy) -2-methylaniline, N , N, N ′, N′-tetraglycidyl-1,3-benzenedi (methanamine), N, N, N ′, N′-tetraglycidyl-1,4-benzenedi (methanamine), N, N, N ′, N′-tetraglycidyldiphenylmethanediamine, 4,4′-methylenebis (N, N-diglycidylaniline), 4,4′-me Renbis (N, N-diglycidyl-2-methylaniline), 4,4′-methylenebis (N, N-diglycidyl-3-methylaniline), 4,4 ′-[1,4-phenylenebis (dimethylmethylene)] Bis (N, N-diglycidylaniline), 4,4 ′-[1,4-phenylenebis (dimethylmethylene)] bis (N, N-bisglycidyl-2,6-dimethylaniline), 4,4′- And [(1,4-phenylene) bisoxy] bis (N, N-diglycidylaniline).

As the aromatic glycidylamine type epoxy resin (A2) used in the present invention, N, N-diglycidyl-4- (glycidyloxy) aniline, N, N-diglycidyl-3- (glycidyloxy) aniline, N, N- Diglycidyl-4- (glycidyloxy) -2-methylaniline, 4,4′-methylenebis (N, N-diglycidylaniline), 4,4′-methylenebis (N, N-diglycidyl-2-methylaniline), 4 , 4′-methylenebis (N, N-diglycidyl-3-methylaniline), 4,4 ′-[1,4-phenylenebis (dimethylmethylene)] bis (N, N-diglycidylaniline), 4,4 ′ One or more selected from-[1,4-phenylenebis (dimethylmethylene)] bis (N, N-bisglycidyl-2,6-dimethylaniline) From the viewpoint of heat resistance, 4,4′-methylenebis (N, N-diglycidylaniline), 4,4′-methylenebis (N, N-diglycidyl-2-methylaniline), 4,4 ′ Selected from -methylenebis (N, N-diglycidyl-3-methylaniline), 4,4 '-[1,4-phenylenebis (dimethylmethylene)] bis (N, N-bisglycidyl-2,6-dimethylaniline) It is more preferable to use one kind or a mixture of two or more kinds from the viewpoint of achieving both high toughness and high elastic modulus. These may be used alone or in combination of two or more, but N, N-diglycidyl-4- (glycidyloxy) aniline, N, N-diglycidyl-4- (glycidyloxy)- One or two or more selected from 2-methylaniline and N, N-diglycidyl-3- (glycidyloxy) aniline, and 4,4′-methylenebis (N, N-diglycidylaniline), 4,4′- Methylene bis (N, N-diglycidyl-2-methylaniline), 4,4′-methylene bis (N, N-diglycidyl-3-methylaniline), and 4,4 ′-[1,4-phenylene bis (dimethylmethylene) The view that the combined use of one or more selected from bis (N, N-bisglycidyl-2,6-dimethylaniline) achieves both heat resistance, high toughness and high elastic modulus Further preferred from the point. In this case, the cured product of the liquid resin composition for semiconductor encapsulation has high toughness and high elasticity, and prevents the occurrence of peeling and cracking of the bump joints and fillets during the temperature cycle test, resulting in a semiconductor device having excellent connection reliability. It is done.

  The total compounding ratio of the epoxy resin (A) in the liquid resin composition for semiconductor encapsulation is preferably 10% by mass or more and 50% by mass or less with respect to the total mass of the liquid resin composition for semiconductor encapsulation, More preferably, it is 15 mass% or more and 35 mass% or less. When it is within the above range, the obtained liquid resin composition for semiconductor encapsulation can achieve good fluidity without lowering the fracture toughness value.

  The weight ratio W (A1) / W (A2) of the epoxy resin (A1) that is liquid at 25 ° C. and the aromatic glycidylamine type epoxy resin (A2) is preferably 1/9 or more and 7/1 or less. More preferably, it is 1/4 or more and 3/1 or less. When the weight ratio W (A1) / W (A2) is within the above range, the obtained liquid resin composition for semiconductor encapsulation may exhibit good heat resistance and fluidity without reducing the fracture toughness value. it can.

As the amine-based curing agent (B) used in the present invention, as long as it contains two or more primary amines or secondary amines capable of forming a covalent bond with the epoxy group in the epoxy resin. In particular, the molecular weight and structure are not limited. Examples of such amine curing agents include aliphatic polyamine compounds such as trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, and m-xylylenediamine. Cycloaliphatic polyamines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane Piperazine type polyamines such as N-aminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphe Sulfone, diethyltoluenediamine, trimethylenebis (4-aminobenzoate), polytetramethylene oxide-di-P-aminobenzoate, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-diethyl- 4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminophenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminophenylmethane 4,4′-bis [N-methylamino] diphenylmethane, 4,4′-bis [N-ethylamino] diphenylmethane, 2,4-diaminotoluene, 1,4-diaminobenzene, 1,3-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, , Aromatic polyamines such as 3,5-triethyl-2,6-diaminobenzene and the like.

These amine-based curing agents may be used alone or in combination of two or more, such as diethyltoluenediamine, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 4,4′-bis. [N-methylamino] diphenylmethane is preferable from the viewpoints of fluidity and storage stability at room temperature, and 3,3′-diethyl-4,4′-diaminodiphenylmethane, 4,4′-bis [
N-methylamino] diphenylmethane is more preferable from the viewpoint of reactivity. Furthermore, since the aspect of this invention is a liquid resin composition for semiconductor sealing used as an underfill material, what exhibits a liquid state at 25 degreeC is more preferable.

  The epoxy resin (A) and the amine curing agent (B) are equivalent to the number of epoxy groups (EP) of the total epoxy resin (A) and the number of active hydrogen groups (H) of the total amine curing agent (B). It is preferable to mix | blend so that ratio (EP) / (H) may be 0.6 or more and 1.4 or less, and it is more preferable to mix | blend so that it may be 0.7 or more and 1.3 or less. When the equivalent ratio is within the above range, sufficient curing characteristics can be obtained when molding the obtained liquid resin composition for semiconductor encapsulation.

As an inorganic filler (C) used for this invention, what is generally used for the semiconductor sealing material can be used.
For example, silicates such as talc, calcined clay, unfired clay, mica, glass, titanium oxide, alumina powder, magnesium oxide, fused silica (fused spherical silica, fused crushed silica), silica powder such as synthetic silica, crystalline silica Oxides such as, carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite Examples include salts, borate salts such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate, and nitrides such as aluminum nitride, boron nitride, and silicon nitride. It may be used in combination. Among these, fused silica, crystalline silica, and synthetic silica powder are preferable because the heat resistance, moisture resistance, strength, and the like of the liquid resin composition for semiconductor encapsulation can be improved. The shape of the inorganic filler is not particularly limited, but the shape is preferably spherical from the viewpoints of viscosity characteristics and flow characteristics.

The maximum particle size and the average particle size of the inorganic filler (C) used in the present invention are not particularly limited, but it is preferable that the maximum particle size is 10 μm or less and the average particle size is 0.1 μm or more and 3 μm or less. By setting the maximum particle size to be equal to or less than the upper limit value, the effect of suppressing partial unfilling or poor filling due to clogging of the inorganic filler when the semiconductor sealing liquid resin composition flows to the semiconductor device is enhanced. . Moreover, by making the said average particle diameter more than the said lower limit, the viscosity of the liquid resin composition for semiconductor sealing falls moderately, and a filling property improves.
As a method for measuring the average particle size of the inorganic filler (C), for example, a numerical value obtained by arithmetic calculation from a particle size distribution obtained by a laser diffraction light scattering method can be used. In addition, as a method for measuring the maximum particle size, for example, a particle size value in which the ratio of the residue on the sieve when the sieve is sieved with a sieve having a predetermined size by a wet sieving method is 0.1% or less is used. it can.

The total blending ratio of the inorganic filler (C) in the liquid resin composition for semiconductor encapsulation is 30% by mass or more and 75% by mass or less, preferably with respect to the total mass of the liquid resin composition for semiconductor encapsulation. Is 40 mass% or more and 75 mass% or less, More preferably, it is 50 mass% or more and 70 mass% or less. When the blending ratio of the inorganic filler (C) is within the above range, the obtained liquid resin composition for semiconductor encapsulation has good fluidity and filler dispersibility (precipitation resistance) without reducing the fracture toughness value. Can be measured.

The liquid resin composition for semiconductor encapsulation of the present invention can further contain a low stress agent (D).
The low stress agent (D) is not particularly limited as long as it makes the liquid resin composition for semiconductor encapsulation high toughness, and those generally used for semiconductor sealing materials can be widely used. For example, ethylene / ethyl acrylate copolymer resin, ethylene / vinyl acetate copolymer resin, butadiene-nitrile rubber, polyurethane, acrylic rubber, acrylonitrile-butadiene rubber, carboxyl group terminal acrylonitrile-butadiene rubber, amino group terminal acrylonitrile-butadiene rubber, vinyl Examples thereof include base terminal acrylonitrile-butadiene rubber, silicone rubber, polyethylene, polypropylene, polybutadiene, epoxidized polybutadiene, silicone rubber, olefin copolymer, nitrile rubber and modified products thereof. These low stress agents may be used alone or in combination of two or more, and epoxidized polybutadiene is preferred from the viewpoint of fluidity and toughness. Moreover, the whole compounding ratio of the low stress agent (D) in the liquid resin composition for semiconductor encapsulation is 0.3 to 5% by weight with respect to the total mass of the liquid resin composition for semiconductor encapsulation. Is preferable, and 0.5 to 3 weight% is more preferable. When the blending ratio of the low-stress agent (D) is within the above range, the cured product of the obtained liquid resin composition for semiconductor encapsulation can achieve good fluidity and high toughness without reducing the elastic modulus. Can do.

  In the liquid resin composition for semiconductor encapsulation of the present invention, as other components other than the above, if necessary, a colorant such as a diluent, carbon black, bengara, titanium oxide, a leveling agent, an antifoaming agent, a coupling Additives such as additives and flame retardants can be used.

  As a method for producing a liquid resin composition for semiconductor encapsulation of the present invention, each component, additive, and the like are dispersed and kneaded using an apparatus such as a planetary mixer, three rolls, two heat rolls, and a laika machine, A method for defoaming under vacuum is exemplified. The viscosity for using the thus obtained semiconductor resin-sealing liquid resin composition as an underfill material is preferably 300 Pa · s or less, more preferably 200 Pa · s or less at 25 ° C.

  Examples of the curing method of the semiconductor sealing liquid resin composition include oven curing and in-line curing. The curing condition of the liquid resin composition for semiconductor encapsulation is preferably 100 to 180 ° C. and cured for 1 hour or more.

The fracture toughness value of the cured product of the liquid resin composition for semiconductor encapsulation of the present invention is 2.0 MPa · m ^ 0.5 or more and 3.5 MPa · m ^ 0.5 or less, more preferably 2.5 MPa · m ^ 0.5 or more and 3.5 MPa · m ^ 0.5 or less. When this range is satisfied, the semiconductor device excellent in connection reliability can be obtained by preventing the peeling of the fillet part and the occurrence of cracks during the temperature cycle test due to high toughness.
The fracture toughness value of the cured product of the liquid resin composition for semiconductor encapsulation of the present invention can be determined by appropriately selecting the structure and the number of functional groups of the epoxy resin, the structure of the amine curing agent, and the amount of filler. It can be 0 or more and 3.5 or less.

The elastic modulus at 240 ° C. measured by the dynamic viscoelasticity measuring apparatus for the cured product of the liquid resin composition for semiconductor encapsulation of the present invention is 120 MPa or more, more preferably 120 MPa or more and 500 MPa or less, and further 150 MPa or more and 500 MPa or less. preferable. When this range is satisfied, the cured product of the liquid resin composition for semiconductor encapsulation becomes highly elastic, and the semiconductor device having excellent connection reliability can be obtained by preventing the peeling of the bump joint and cracking during the temperature cycle test.
The elastic modulus at 240 ° C. measured with the dynamic viscoelasticity measuring apparatus of the cured product of the liquid resin composition for semiconductor encapsulation of the present invention is the structure and the number of functional groups of the epoxy resin, the structure of the amine curing agent, and the filling. By appropriately selecting the material blending amount, it can be set to 120 MPa or more.

It is preferable that the glass transition temperature measured in the dynamic viscoelasticity measuring apparatus of the hardened | cured material of the liquid resin composition for semiconductor sealing of this invention is 120 to 150 degreeC, and 130 to 150 degreeC is more preferable. When this range is satisfied, a semiconductor device having excellent connection reliability can be obtained by preventing peeling of the bump joint and cracking during the temperature cycle test.
The glass transition temperature measured in the dynamic viscoelasticity measuring device of the cured product of the liquid resin composition for semiconductor encapsulation of the present invention is the structure and the number of functional groups of the epoxy resin, the structure of the amine curing agent, and the amount of fillers Can be appropriately set to 120 ° C. or higher and 150 ° C. or lower.

The semiconductor device according to the present invention includes an electronic component and an electronic component mounting substrate, and the electronic component and the electronic component mounting substrate are electrically connected and joined by conductive bumps or wires. A form in which the substrate for mounting components, all of the electrical joints, or part of the electrical joint and the electronic components, part of the substrate for mounting electronic components are sealed, protected, and embedded with the liquid resin composition for semiconductor encapsulation of the present invention If there is no particular limitation. Although the usage method of the liquid resin composition for semiconductor encapsulation of this invention is not specifically limited, The method of apply | coating using potting, printing, and a capillary phenomenon, and heat-curing is common. Such semiconductor devices include flip chip semiconductor packages,
There are a cavity down type BGA, a TAB (Tate Automated Bonding) type BGA, a CSP, and a driver chip around a display element such as a liquid crystal or LED light emitting element.

The most suitable use of the liquid resin composition for semiconductor encapsulation of the present invention is a flip chip type semiconductor package. A flip-chip semiconductor package is an electronic component and an electronic component mounting board that are electrically connected via solder bumps. Solder bumps are often made of an alloy containing tin, lead, silver, copper, bismuth, etc. As a method of electrical connection, a flip chip bonder or the like is used to connect metal pads and electronic components on an electronic component mounting board. After aligning the solder bumps on the component, the solder bumps are heated to the melting point or higher by using an IR reflow device, hot plate, or other heating device, and the metal pads and solder bumps on the electronic component mounting board are melted. Made by joining. At this time, a solder paste or a solder layer having a relatively low melting point may be formed on the metal pad portion on the electronic component mounting substrate. The electrically connected semiconductor device has a form in which metal bumps exist in a columnar shape in a parallel gap between the electronic component and the electronic component mounting substrate.
The method of using the liquid resin composition for semiconductor encapsulation of the present invention utilizes the capillary resin or pressure difference of the liquid resin composition for semiconductor encapsulation of the present invention in the parallel gap between the electronic component and the substrate for mounting the electronic component. Then, a method of sealing by flowing, filling and filling, and then sealing, applying a liquid resin composition for semiconductor sealing to the electronic component mounting substrate or electronic component by printing or drawing in advance, There is a method in which the electronic component mounting base is joined and heated to the melting point of the solder bump or higher to perform electrical connection and resin curing in a lump, but any method may be used.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to description of these Examples at all. Unless otherwise specified, the amount of each component described below is part by mass.
The materials used in the examples or comparative examples are as follows.

Epoxy resin 1: bisphenol F type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YDF-8170, epoxy equivalent 160 g / eq)
Epoxy resin 2: bisphenol A type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YD-8125, epoxy equivalent 172 g / eq)
Epoxy resin 3: Epoxy resin represented by formula (4) (4,4′-methylenebis (N, N-diglycidylaniline), manufactured by Mitsubishi Chemical Corporation, JER604, epoxy equivalent 106 g / eq)

Epoxy resin 4: Epoxy resin represented by formula (5) (4,4 ′-[1,4-phenylenebis (dimethylmethylene)] bis (N, N-bisglycidyl-2,6-dimethylaniline), SHELL CHEMICAL (USA), HPT1072, epoxy equivalent 15
7g / eq)

  Epoxy resin 5: Epoxy resin represented by formula (6) (N, N-diglycidyl-4- (glycidyloxy) aniline, manufactured by Mitsubishi Chemical Corporation, JER630, epoxy equivalent 98 g / eq)

Amine-based curing agent 1: 3,3′-diethyl-4,4′-diaminodiphenylmethane (Nippon Kayaku Co., Ltd.) in which R5 is a diethyl group, R6 is a hydrogen atom, and the average of n3 is 1.2 in formula (3) Kayahard AA, amine equivalent 63.5 g / eq)
Amine-based curing agent 2: 4,5′-bis [N-methylamino] diphenylmethane (Sanyo Kasei Kogyo Co., Ltd.) in which R5 is a hydrogen atom, R6 is a methyl group, and the average of n3 is 1.6 in formula (3) Co., Ltd., T-12, amine equivalent: 116 g / eq)
Amine-based curing agent 3: diethyltoluenediamine (manufactured by Mitsubishi Chemical Corporation, JER Cure W, amine equivalent 47.5 g / eq)

Curing accelerator: 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., Curesol 2P4MZ)
Low stress agent: Epoxidized polybutadiene (manufactured by ADEKA, BF-1000)
Colorant: Carbon black (Mitsubishi Chemical Corporation MA600)
Diluent: ethylene glycol mono-normal-butyl ether acetate (Tokyo Chemical Industry Co., Ltd., BCSA)
Coupling agent: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403)
Inorganic filler 1: synthetic spherical silica (manufactured by Admatechs, SO-E2, average particle size 0.5 μm)
Inorganic filler 2: Synthetic spherical silica (manufactured by Admatechs, SO-E5, average particle size 1.5 μm)

Example 1
The following components were mixed using a planetary mixer and three rolls, and vacuum defoamed to obtain a liquid resin composition for semiconductor encapsulation.
Epoxy resin 1 25.0 parts by mass Epoxy resin 2 75.0 parts by mass Amine-based curing agent 1 49.7 parts by mass Low stress agent 5.0 parts by mass Colorant 0.1 part by mass Diluent 2.0 parts by mass Coupling Agent 5.0 parts by mass Inorganic filler 1 150.2 parts by mass Inorganic filler 2 150.2 parts by mass The obtained liquid resin composition for semiconductor encapsulation was evaluated for the following items. The evaluation results are shown in Table 1.

  Initial viscosity: Measured using a TVE viscometer / model name TVE-33 manufactured by Toki Sangyo Co., Ltd. under conditions of 25 ° C. and 5 rpm. The unit is Pa · s.

  Fracture toughness value: Measured according to the KIc method standardized by ASTM D5045-91. The liquid resin composition for semiconductor encapsulation was 90 mm long, 14 mm high, and 7 mm thick, with a notch with a depth of 6 mm in the center in the length direction, and cured at 150 ° C. for 2 hours. Further, a 1 mm deep scratch was made on the notch tip of the cured product with a razor, and 3 points were measured using a UCT-5T type Tensilon manufactured by Orientec Co., Ltd. at a measurement temperature of 25 ° C., a speed of 2 mm / min, and a fulcrum distance of 58 mm. A bending test was performed to calculate the fracture toughness value (K1c). The unit is MPa · m ^ 0.5.

-Glass transition temperature: After hardening the liquid resin composition for semiconductor sealing at 150 degreeC x 2 hours, the test piece of 10x50x1mm was obtained by cutting. Using the dynamic viscoelasticity measuring device (Seiko Instruments Co., Ltd., DMS6100), this test piece was tan δ under the conditions of a tensile method, a frequency of 10 Hz, a heating rate of 5 ° C./min, and a measurement temperature region of 20 ° C. to 300 ° C. Tan
The temperature at which the peak of δ appears was defined as the glass transition temperature. The unit is ° C.

  -Elastic modulus: After hardening the liquid resin composition for semiconductor sealing at 150 degreeC x 2 hours, the test piece of 10x50x1mm was obtained by cutting. This test piece was measured using a dynamic viscoelasticity measuring apparatus (Seiko Instruments Co., Ltd., DMS6100) under the conditions of a tensile method, a frequency of 10 Hz, a temperature increase rate of 5 ° C./min, and a measurement temperature region of 20 ° C. to 300 ° C. And the storage elastic modulus at 240 ° C. was read. The unit is MPa.

A semiconductor device was produced by flowing and sealing a liquid resin composition for semiconductor encapsulation into a gap between a circuit board and a semiconductor chip joined by solder bumps, and the following items were evaluated.
The components of the semiconductor device used for the evaluation are as follows. The semiconductor chip is a 15 mm x 15 mm x 0.8 mmt formed by using lead as a solder bump and a Sn / Ag / Cu composition as a solder bump on a PHASE-2TEG wafer manufactured by Hitachi VLSI. Cut and used.
As a circuit board, a 0.4 mmt glass epoxy board equivalent to FR5 manufactured by Sumitomo Bakelite Co., Ltd. is used as a base, and a solder resist PSR4000 / AUS308 manufactured by Taiyo Ink Mfg. Co., Ltd. is formed on both sides, and the above solder is used on one side. A gold-plated pad corresponding to the bump arrangement was cut into a size of 50 mm × 50 mm and used.
TSF-6502 (manufactured by Kester, rosin flux) was used as a flux for connection.

  In assembling the semiconductor device, a flux is uniformly applied to a sufficiently smooth metal or glass plate using a doctor blade to a thickness of about 50 μm, and then a flip chip bonder is used to form a semiconductor chip having solder bumps mounted on the flux film. The solder bump mounting surface side was lightly contacted and then released to transfer the flux to the solder bump. Next, after aligning the solder bumps of the semiconductor chip and the pads of the circuit board, the semiconductor chip was pressed onto the circuit board. Next, IR reflow treatment (peak temperature 260 ° C.) was performed, and solder bumps were melted and produced. Cleaning was performed using a cleaning liquid after the melt bonding. The filling and sealing method of the liquid resin composition was carried out by heating the prepared semiconductor device on a hot plate at 110 ° C., applying the prepared liquid resin composition on one side of the semiconductor chip, filling the gap, and then filling the gap at 150 ° C. The liquid resin composition was heated and cured in an oven for 120 minutes to obtain a semiconductor device for evaluation test.

  -Flow time: When assembling the semiconductor device, the manufactured semiconductor device is heated on a hot plate at 110 ° C., and the liquid resin composition prepared on one side of the semiconductor chip is applied until the gap is completely filled. Time was measured and taken as flow time. The unit is seconds.

  Reflow resistance: Semiconductor device 20 in which the above-described semiconductor device was subjected to a JEDEC level 3 moisture absorption treatment (treated at 30 ° C. and 60% relative humidity for 168 hours) and then subjected to IR reflow treatment (peak temperature 260 ° C.) three times. About each, the presence or absence of peeling of the liquid resin composition inside the semiconductor device was confirmed with an ultrasonic flaw detector. The criteria for determining reflow resistance were ◯ when no peeling occurred, Δ when the peeling rate was less than 20%, and x when the peeling rate was 20% or more. ○ and △ are at a level where there is no practical problem.

Temperature cycle test: The above semiconductor device was subjected to a temperature cycle treatment of (−55 ° C./30 minutes) and (125 ° C./30 minutes). About 20 packages, the adhesion state of the interface between the semiconductor element and the cured resin resin composition is observed with an ultrasonic flaw detector every 1000 cycles, and the rate of occurrence of peeling or cracks occurring in the fillet portion or bump bonding portion [ (Number of peeled or cracked packages) / (total number of packages) × 100] was calculated. Units%. The judgment criteria of the temperature cycle test were ○ for those where peeling or cracking did not occur, Δ for peeling or cracking less than 20%, and x for peeling or cracking 20% or more. △,
About x thing, it was described whether the part which peeling or the crack generate | occur | produced is a fillet part or a bump junction part. ○ and △ are at a level where there is no practical problem.

Examples 2-17, Comparative Examples 1-4
According to the composition of Table 1, Table 2, and Table 3, a liquid resin composition for semiconductor encapsulation was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1, Table 2, and Table 3.

  Examples 1 to 17 include an epoxy resin (A1) that is liquid at 25 ° C., an aromatic glycidylamine-type epoxy resin (A2), an amine-based curing agent (B), and an inorganic filler (C). It is a resin composition, which is obtained by changing the type of epoxy resin (A1) that is liquid at 25 ° C., changed by the type of aromatic glycidylamine type epoxy resin (A2), and epoxy resin that is liquid at 25 ° C. ( A1) and aromatic glycidylamine type epoxy resin (A2) are used in different ratios, but all have excellent balance of fluidity, fracture toughness and elastic modulus, and connection reliability during temperature cycle test Thus, a semiconductor device having high reflow resistance was obtained.

On the other hand, in Comparative Examples 1 to 4, any one of fluidity, fracture toughness value, and elastic modulus was inferior, and connection reliability and reflow resistance during a temperature cycle test were also inferior.
According to the present invention, there is provided a liquid resin composition for semiconductor encapsulation excellent in the balance of fluidity, fracture toughness value, and elastic modulus, and a semiconductor device excellent in reflow resistance having high connection reliability in a temperature cycle test using the same. Can be obtained.

Claims (9)

  A liquid resin composition for semiconductor encapsulation containing an epoxy resin (A), an amine curing agent (B), and an inorganic filler (C), wherein the epoxy resin (A) is liquid at 25 ° C. A liquid resin composition for encapsulating a semiconductor, comprising an epoxy resin (A1) and an aromatic glycidylamine type epoxy resin (A2), wherein the content of the inorganic filler (C) is 30 wt% or more and 75 wt% or less. A fracture resin toughness value of 2.0 MPa · m ^ 0.5 or more and 3.5 MPa · m ^ 0.5 or less is a liquid resin composition for semiconductor encapsulation.   The liquid resin composition for semiconductor encapsulation according to claim 1, wherein an elastic modulus at 240 ° C. measured by a dynamic viscoelasticity measuring apparatus for a cured product of the liquid resin composition for semiconductor encapsulation is 120 MPa or more.   3. The liquid resin composition for semiconductor encapsulation according to claim 1, wherein a glass transition temperature measured by a dynamic viscoelasticity measuring device for a cured product of the liquid resin composition for semiconductor encapsulation is 120 ° C. or higher and 150 ° C. or lower. . The liquid resin composition for semiconductor encapsulation according to any one of claims 1 to 3, wherein the aromatic glycidylamine type epoxy resin (A2) contains a compound represented by the following general formula (1).

(In General Formula (1), R1, R2, and R3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m1 is an integer of 0 to 4, and n1 is 0 to 0. (It is an integer of 5.) The semiconductor according to any one of claims 1 to 4, wherein the aromatic glycidylamine type epoxy resin (A2) includes a compound represented by the following general formula (1) and a compound represented by the following general formula (2). Liquid resin composition for sealing.

(In General formula (2), R4 is a hydrogen atom or a C1-C6 hydrocarbon group mutually independently, and m4 is an integer of 0-4.) The liquid resin composition for semiconductor encapsulation according to any one of claims 1 to 5, wherein the amine-based curing agent (B) contains a compound represented by the following general formula (3) and / or diethyltoluenediamine.

(In General Formula (3), R5 and R6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, m5 is an integer of 0 to 3, and n3 is an integer of 0 to 10. (It is an integer.)   Furthermore, the liquid resin composition for semiconductor sealing of any one of Claim 1 thru | or 6 containing a low stress agent (D).   The liquid resin composition for semiconductor encapsulation according to claim 1, wherein the low stress agent (D) contains epoxidized polybutadiene.   A semiconductor device including an electronic component and an electronic component mounting substrate, and having a gap between the electronic component and the electronic component mounting substrate, wherein the gap between the electronic component and the electronic component mounting substrate is 9. A semiconductor device, wherein the semiconductor device is filled and joined with a cured product of the liquid resin composition for sealing a semiconductor according to claim 1.